Issues with first roll of non expired film

[knotimpressed]

That's an approximate date, but yes, the stabilizers are "baked in" for color emulsions made over roughly the past twenty years, meaning there's no need for stabilizer with current-date or recently expired C-41 films. If you have film that needs stabilizer, however, after the post-blix wash, and before the final rinse is the correct sequence. I'd expect the final rinse to remove enough of the hexamine from the film to stop crystals from forming following the stabilizer.

Honestly, I don't recommend C-41 replenishment for a home worker -- the rate is too variable (depends on type of film processed, as well as roll length/area) and to really keep your process in line you also have to run control strips regularly (which can be hard to find in date) and be able to read them (a learned skill, and from my understanding also requires instruments). Further, I don't know where you'd buy either Kodak or Fuji C-41chemicals in Canada -- lots of stuff seems harder to get or more expensive there than south of the border, and even here in the States Flexicolor can be hard to come by for a consumer (labs get it from distributors who won't even talk to the likes of us, we're dependent on such companies being willing to resell some of what they buy). There's only one reliable source I know in the US for the full Flexicolor line, for instance -- and you'll drop a pretty good wad getting everything first time out, though over time it's the Developer Replenisher you'll use the most of, even if you're one-shotting the color developer as is often recommended.

On the other hand, CD-4 might be hard to come by in the Great White North, too. If you can find a source of that at a cost you can live with, however, I'd be happy to post the Dignan recipe as I've used it.

Ah I see, my kit doesn’t have any final rinse and I don’t have any so stabilizer is the last step for me until I get some. Thanks for telling me about that, all the threads I’ve read are older and no one has mentioned it.

Also if CD4 is the hardest part, I think I’m in luck. Argentix.ca has it in stock, and actually most of the Flexicolor Chems. They list 100 grams for $28 CAD (21 USD). Is that a good price? How hard are the other components to get?

Also how specific is the chemistry in terms of making the working solutions? Are specific temperatures and times needed, or is it just dissolve it all and go?

I’d love to see the recipe if you have it.

 

[Donald Qualls]

Honestly, I don't recall what I paid for my CD-4 when I bought it from Photographer's Formulary or Artcraft around 2006. But here's the recipe I used for the Dignan developer:

Dignan NCF-41 -- Two-Bath C-41 Color Developer

This developer was originally published by Patrick D. Dignan in the November-December 1995 issue of Phototechniques magazine. I've modified the Bath B very slightly to use more readily available chemicals and to reflect my own experience.

Like most two-bath developers, little or no development takes place in Bath A; the developer permeates the emulsion, however, and the chemical thus carried over into Bath B does the work, developing essentially to exhaustion in the time allotted for Bath B. This makes the process relatively insensitive to temperature variations; Dignan recommends 75° F, but my experience shows that, because it develops to exhaustion, the developer works effectively the same over a range of temperature from about 70° F up to at least 85° F. Also like most two-bath systems, the Bath A has a very long life; I made up a liter initially, and have processed equivalent of about ten rolls over two months with no change in results (though I'm about to make up some more Bath A to use in replenishing the working solution, much as I'd use fresh Diafine to replenish the solutions in use). The Bath A solution does tend to discolor over time with dyes washed out of the film, but this doesn't seem to cause any change in working characteristics.

Bath B is to be used one-shot -- it contains no preservative, and in fact is essentially just an alkaline solution of the proper pH with some restrainer added to control fog. Dignan originally called out both potassium bromide and benzotriazole, but since I didn't have any benzotriazole (and the notes I found with the formula suggested Dignan had used the developer without it), I doubled his level of potassium bromide and found the developer worked fine that way. This B bath is very cheap, so it's not painful to toss it down the drain after use.

I calculate that despite paying $24 for 100 grams of CD-4 to make the Bath A, this developer costs me around a nickel a roll to use because of the long life of Bath A and low cost of Bath B -- as was always the case, it's the bleach that's expensive (commercial bleach is $26 a gallon and is used as it comes, undiluted, a gallon good for about 32 rolls), but I'll soon be testing a homemade ferricyanide bleach. C-41 fixer and final rinse are so cheap I doubt I'll ever bother trying to make up substitutes -- the fixer is similarly priced to B&W rapid fixer, and if you can find no-starter-needed third party C-41 fixers, they're typically even cheaper than the Kodak Flexicolor Fixer, while Flexicolor Final Rinse is similarly priced and used at similar dilution to PhotoFlo (1+110, or 9 ml to make a liter of working solution) -- again, not really worth seeking a substitute.

It is strongly recommended to increase bleach and fixing times over those given in the usual C-41 documentation; due to lower temperature, these baths will work slower than they would at the canonical 100° F. I've found that Flexicolor Bleach III gets the job done in ten minutes, even so, and I've been giving ten minutes in fixer as well. However, you can neither overbleach nor overfix C-41; both processes should be carried to completion, and no harm can be done by leaving the film in these baths longer (within reason).

Bath A

300 ml Distilled Water
0.5 g Sodium Bisulfite
5.5 g CD-4
4.5 g Sodium Sulfite (anhydrous)

Distilled water to make 500 ml
pH at 75° F should be 6.5 or lower (though I haven't tested mine, having no way to check pH)

Bath B
500 ml Distilled or Filtered Water
45 g Sodium Carbonate (monohydrate) aka washing soda
1 g Potassium Bromide

Water to make 1 liter
pH with original potassium carbonate is listed as 11.8 at 75° F; sodium carbonate should give 11.6 and works just fine

Bath Time
Bath A 3 minutes, return to storage container
Bath B 6 minutes, pour down drain
Times as originally given include 15 seconds pour-out and drain time, i.e. start pouring off when fifteen seconds remain. In practice, like all two-bath systems, Bath A time is grossly non-critical as long as a minimum of three minutes is given; one needs only to ensure enough time for the developer to completely saturate the emulsion. Further, Bath B cannot overdevelop because the developer carried over in the emulsion exhausts in the six minutes given (proved by lack of change in development over a fifteen degree temperature range).

I recommend use of a weak acid stop bath between Bath B and the bleach bath; Flexicolor Bleach, at least, is acidic enough to generate significant gas by reaction with the carbonate alkali (enough to pop the inversion cap off my stainless tanks), and stop bath leaks are far less worrisome than the same with either Flexicolor or ferricyanide bleach (plus, if you use ferricyanide bleach, it can't be significantly acidic, so a separate stop bath might be prudent to ensure development is stopped before bleaching begins).​

As you can see, nothing exotic here, and the original 5.5 g of CD-4 will last a dozen or more rolls if you're processing 35mm one roll at a time (you lose a few milliliters of Bath A with each roll you process, carried over into Bath B to do the work) and Bath A self-replenishes at any desired rate -- just need to make up volume so it covers your film. I made this to a full liter, and made up Bath B as needed (you could even make it immediately before processing). You'd get 9 liters of Bath A from that 100 g purchase of CD-4, which is enough to process hundreds of rolls. Mixing it only to the volume you need to fill the largest tank you'll use and have a little reserve will help with longevity, since the dry chemicals will keep for many years, while I don't know how long the Bath A will last (at least several months, but the bottle I still have in my shed after 12 years of storage is the same color as when I last used it).

Also, I note that your CD-4 is only a few dollars more than I paid (maybe even about the same, allowing for your smaller dollars), so my cost calculations above mostly still stand. Mixing your own is almost always the cheapest way to go, unless you need something exotic that's hard to get and impossible to substitute. I've had confirmation recently that ferricyanide bleach (with potassium bromide added, so it rehalogenates) works fine with both Kodak and Fuji films, you can get away with any alkaline rapid fixer (though C-41 fixer is cheapish), and C-41 Finals Rinse isn't too hard to find. Argentix probably also carries potassium ferricyanide, and if they have CD-4 will surely have the sulfite, bisulfite, and potassium bromide.

You'll have to test for yourself or do some research to find the bleach time needed for ferricyanide bleach, as I never got around to using it before getting crowded out of my darkroom back in 2008 -- but you should be able to get a starting point by testing on a fully fogged and developed clip of B&W film; when the black has all gone back to the milky color of halide, the bleach has done its work.

 

[knotimpressed]

Honestly, I don't recall what I paid for my CD-4 when I bought it from Photographer's Formulary or Artcraft around 2006. But here's the recipe I used for the Dignan developer:

Dignan NCF-41 -- Two-Bath C-41 Color Developer.​

​

I'm really really grateful for all of your help, getting this much information off google takes hours normally. I'm a little busy right now and I'll do some of my own research to not pester you with unnecessary questions, so sometime tomorrow I'll probably respond with whatever else is left.

In terms of bleaching times, am I correct in thinking going a little bit over on the bleach time isn't that much of an issue? For Blix I know you can go over but I don't have any experience with a two solution system.

Thank you again, I'll be back tomorrow hopefully.

 

[MattKing]

The old stabilizers included three things - a component that stabilized the dyes, a bactericide to help extend the life of the processed negative (some of the parts in a developed colour negative are attractive to bacteria) and a surfactant that helped film to dry without water marks.
After the dye stabilization was incorporated earlier in the process, the stabilizer was replaced with final rinse which included the remaining two things - a bactericide to help extend the life of the processed negative (some of the parts in a developed colour negative are attractive to bacteria) and a surfactant that helped film to dry without water marks.
You want to still include both the bactericide and the surfactant in the last solution to contact the film before drying.

 

[Mr Bill]

I'm a couple days behind, so just trying to catch up a bit with a post largely written back then...

The cost of messing up a roll of expired film is way less than messing up the camera (Shutter curtains don’t like being jabbed with scissors), or messing up the way the film goes onto the take up reel.

I should be more clear. I'd take the film out of the camera before cutting. I'm just trying to make the point that you know exactly where the frame ends. Another way to do this would be to do a partial load in the darkroom; start film in the takeup in the light, holding the cassette in your hand. Wind the film until it pulls the cassette lip beyond the film gate. Then go into the darkroom and pull the cassette back until it fits into the camera and you can close the back; an unexposed frame should now be in the film gate.

Fwiw I'd probably just develop by hand in the dark rather than try loading it on a reel. If you have a friend out in the light they can call out the developing time. Just hold the end of the film above the tank and wiggle the submerged end around a bit. If you need a better holder, to keep your fingers out of the developer, a spring loaded wooden clothes pin would probably work. We used to use disposable locking forceps in our chem lab for holding a variety of things; they'd work great if you have a friend in some lab class that uses them.

You make it seem like one shot developer is way more expensive than other options, is that what I’m using though? I thought one shot only developed one batch of film, where as mine develops 12 rolls before being exhausted.

Well, yeah, I'm using the term loosely to mean having a batch of developer, using it for whatever recommended rolls, and then discard. So yeah, you could stretch out the usage for multiple rolls. But here's two issues with that: first, as you develop more rolls the activity of the developer gradually goes down, so the question is, how long can I go before I decide that it's unacceptably bad? Second, the developer solution you are processing in should properly have restrainers added to it in the form of a "starter solution." (If you don't do this it will be too active.) So, assuming that you are starting out with a developer "replenisher" this means that every time you mix a batch, using a starter solution, you are effectively knocking down the "developing power."

Now, the alternative is a replenished system, which you are apparently just finding out about. Now these get more complicated because you have to "monitor" the results; maybe your activity is falling off so you need to increase the replenishment rate; you need a way to know if this needs to be done. But all the details aside, here's the benefit: the developing solution always remains in a good condition. There's no running until it gets "bad." It remains equally good all the time, never changing activity. If you look up recommended replenishment rates (see Kodak's Z-131 manual) you can calculate how far a unit of developer "replenisher" will go. See my post here: https://www.photrio.com/forum/threa...-out-of-kodak-flexicolor.175962/#post-2291093

Basically, what I said is roughly 18 to 20 rolls per liter of developer replenisher.Or, with LORR developer replenisher, about double that - roughly 36 to 40 rolls per liter of LORR replenisher. Now remember, this is while keeping the standard activity level. Activity is NOT falling off as you go along.

Now you might wonder, why doesn't everybody use LORR replenished systems? Well, I dunno; maybe they don't understand how it works. Or maybe they figure it's too complicated to keep "in control." Or maybe the savings are too small to be worth the extra trouble for them. Or maybe they use Jobo rotary processors, which essentially "kill" the developer with oxidation in short order. A couple things should be said about the downside of such a replenished system. First, you can't have all of the savings in your first batch - you have to start out with one batch of normal tank solution, just like the "single use" batch system. The savings start with the first replenisher batch. Now, in all fairness, at the end of whatever processing run you decide to do, you still have a batch of developer solution that you COULD use until it degrades too far, just like the system you're using now. A second issue is that it will gradually build up sludgy crap that you ought to filter out periodically. And finally, if you get too much oxidation it will still go bad.

 

[Mr Bill]

A few more comments on the "stabilizer" and "final rinse" situation: there was a long-time poster on this site, who sadly passed away earlier this year, who went by the name of "Photo Engineer," or simply PE (It was a great loss to photrio in particular, and to many photo enthusiasts looking for a deeper insight into films and photochemistry, in general.) His name was Ron (Rowland) Mowrey, and he spent years deep inside of Kodak, Rochester, doing development work on color films and chemistry. But unlike many others, when he retired he spent considerable time sharing some of his knowledge and experience with enthusiasts, in particular on this website.

But I digress. Some years ago PE made an extended post which he intended to be the definitive rundown on so-called stabilizers. First a quick primer on modern color films: they essentially have three sets of color-sensitive layers: one sensitive to bluish light, one to greenish light, and one to reddish light. Each layer has a generous supply of so-called "color couplers," which can loosely be seen as one-half of a dye molecule; they are NOT colored dyes, but can become so if they couple with the right chemical. The color couplers in each layer are different, so each layer forms its own specific color when it couples. Now, the chemical which specifically reacts, couples, with a dye coupler is an oxidized developer molecule. The developer becomes oxidized when it "develops" part of a silver image (which has been exposed to light), and the oxidized developer almost immediately reacts with a nearby (on a microscopic scale) color coupler, forming an actual color dye in the film.

Now, there was a problem with earlier dye couplers in that some of the unreacted (unused) couplers COULD react with the dyes formed, and thus degrade the dye image. So the normal cure was a final bath in a "stabilizer" solution to "stabilize" the image. For color films the stabilizing component was formaldehyde, which reacted with the unused color couplers, whereupon the could no longer affect the colored dyes.

Somewhere around the late 1970s(?) the US enacted stricter laws under OSHA to not only better protect employees in a "workplace," but to also make it possible to know exactly what potentially hazardous chemicals they were exposed to. This was known as the "Right to Know law," and mandated that the employers must obtain MSDS, material safety data sheets, for all such chemicals, plus specifically train the employees on how to read same. I'm sure that other parts of the world were doing similar; I don't know who was first, etc., only that this was something of a "movement."

As a result of this sort of thing, formaldehyde was becoming known as a potential problem, especially in decentralized photofinishing, such as one-hour labs. In large scale labs, such as where I worked, this wasn't much of an issue; we could easily put in exhaust systems, etc., we had the expertise. In fact, my department specifically oversaw this sort of thing, including putting togethers the OSHA training programs.

Some of the aftermarket chem makers even did things like substitute different aldehydes. But ultimately the C-41 films were redesigned.

Back to PE's post on the matter. He said that insidecof EK there was a major push, in color neg films, to replace the problematic dye couplers. Once this was done (I think that the Portra films, just prior to the year 2000, were among the first), there was no longer a need for formaldehyde in C41 stabilizer. They continued to use it for some years, in order to deal with all of the older consumer films sitting in cameras for years, etc. Not to mention other film makers, which I don't know what their products needed. But for the modern Kodak products, formaldehyde was no longer needed. Now, formaldehyde had a second property, in that it helped keep microorganisms from eating the gelatin in the emulsion. So a "final rinse" was used in place of the "stabilizer," and it contained some sort of biocide as well as a wetting agent.

PE went on to explain that the reversal films, aka "slides," did NOT get a coupler redesign program (it was a major R&D undertaking), so that reversal films still DO need a formaldehyde-containing stabilizer. But the chemistry was redesigned so that, rather than using straight-up formaldehyde that can readily escape into the air, they used some sort of precursor that would essentially release formaldehyde, as needed, to "stabilize" the film.

This should link to PE's post:
https://www.photrio.com/forum/threa...-hope-on-color-stabilzers.89149/#post-1191872

 

[knotimpressed]

Matt and Bill, thank you so much for your help. Life's been a bit busy the past few days, my apologies for the slow reply.

I'm going to run a test piece of film tonight, to check the developer and the light leaks, hopefully. I'm going to do a long ish piece so I can get it onto the reel easier, and then develop in the tank. That way, I can see both how ruined the developer is, and see if the light leak was a one off or is still there. If no image develops, I'll just run another strip to check the light leaks(in the good developer).

In terms of the developer, I'll price out a more DIY option with mixing my own 2 bath developer, and a plain LORR system. I want to stick with this, but other commitments may get in the way so ideally I'll go with whichever system is more stable in the long term, so I can use it over a longer period.

I don't think I'll be replying for a while, unless I have puzzling results I can't sort out, or if any of you care to know how a stranger fixed their light leak issue lol

Until then!